Pixelated photoresists
A deliberately engineered placement and size constraint (molecular weight distribution) of photoacid generators, solubility switches, photoimageable species, and quenchers forms individual pixels within a photoresist. Upon irradiation, a self-contained reaction occurs within each of the individual pixels that were irradiated to pattern the photoresist. These pixels may take on a variety of forms including a polymer chain, a bulky cluster, a micelle, or a micelle formed of several polymer chains. Furthermore, these pixels may be designed to self-assemble onto the substrate on which the photoresist is applied.
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1. Field of the Invention
The present invention relates to the field of photolithography to form integrated circuits and more particularly to the field of photoresists used in photolithography.
2. Discussion of Related Art
Photolithography is used in the field of integrated circuit processing to form the patterns that will make up the features of an integrated circuit. A photoresist is employed as a sacrificial layer to transfer a pattern to the underlying substrate. This pattern may be used as a template for etching or implanting the substrate. Patterns are typically created in the photoresist by exposing the photoresist to radiation through a mask. The radiation may be visible light, ultraviolet light, deep ultraviolet light, and extreme ultraviolet (EUV) light, or an electron beam. In the case of a “direct write” electron beam, a mask is not necessary because the features may be drawn directly into the photoresist. Most photolithography is done using chemically amplified systems or nonchemically amplified systems (e.g. “i-line”). In the i-line method an additive in the photoresist becomes soluble in developer when irradiated and the additive also renders surrounding species soluble and thus the exposed photoresist may be removed by a developer. In the chemical amplification (CA) method the radiation applied to the photoresist causes the decomposition of a photo-acid generator (PAG) that causes the generation of a small amount of acid catalyst throughout the exposed resist. The acid in turn causes a cascade of chemical reactions either instantly or in a post-exposure bake that increase the solubility of the resist such that the resist may be removed by a developer. An advantage of using the CA method is that the chemical reactions are catalytic and therefore the acid is regenerated afterwards and may be reused, thereby decreasing the amount of radiation required for pattern formation in the resist and thus enabling the use of shorter wavelengths of light such as EUV that are produced by weaker light sources. The photoresist may be positive tone or negative tone. In a positive tone photoresist the area exposed to the radiation will define the area where the photoresist will be removed. In a negative tone photoresist the area that is not exposed to the radiation will define the area where the photoresist will be removed. The CA method may be used with either a positive tone photoresist or a negative tone photoresist.
As the scale of the dimensions of the structures formed by etching materials masked by photoresist materials are scaled down, the performance of the photoresist materials must increase. For one thing, critical dimension (CD) control must be increased. As dimensions of the structures are scaled down, the amount of permissible error in the critical dimensions of the structures decreases. Also, the line width roughness of the areas etched must be minimal to accommodate for smaller dimensions and improved device performance. The defectivity of the photoresists must also be minimized. Similarly, collapse of the photoresist must be minimized. Defectivity and collapse are believed to occur, in part, when the mixture of the photoresist components are not uniformly distributed which results in uneven performance within the photoresist and thus the photoresist may not be properly patterned. Each of these issues poses challenges to chemically amplified (CA) resists.
To deal with these issues in the past, the choice of photoacid generator (PAG), as well as control of polymer molecular weight, polymer primary structure, molecular weight distribution, polymer side groups's structure and as well as quencher and other additives' structures and these species' relative ratios, in addition to the solvent system, are used to modulate the resulting performance of the photoresist formulation. Many of these approaches address the issue of preventing the PAG from diffusing beyond the region irradiated to reduce line width roughness and improve CD control. Approaches that address controlling the diffusion of the PAG include using a bulky PAG such as triphenylsulfonium perfluorooctanyl sulfonate (PFOS) to create upon photolysis at the appropriate wavelength a bulky PAG that will diffuse only a short length. The minimization of the diffusion of the PAG has also been taken one step further by attaching the PAG to a side chain of the photoimageable species, such as a polymer. Preventing the diffusion of the photoacid has also been approached by attaching the quencher to the photoimageable species. The drawback to these approaches is that the components within the photoresist are still not evenly distributed and the resulting system's constituent species are not all the same size. The lack of even distribution and uniformity in the size of the components may cause the photoacid to diffuse too much or too little before it is scavenged by a quencher. This may reduce the photospeed of the photoresist, and cause line roughness and loss of CD control.
Described herein are several embodiments of pixelated photoresists and methods of using the pixelated photoresists. In the following description numerous specific details are set forth. One of ordinary skill in the art, however, will appreciate that these specific details are not necessary to practice embodiments of the invention. While certain exemplary embodiments of the invention are described and shown in the accompanying drawings, it is to be understood that such embodiments are merely illustrative and not restrictive of the current invention, and that this invention is not restricted to the specific constructions and arrangements shown and described because modifications may occur to those ordinarily skilled in the art. In other instances, well known semiconductor fabrication processes, techniques, materials, equipment, etc., have not been set forth in particular detail in order to not unnecessarily obscure embodiments of the present invention.
The performance and patterning quality of photoresists may be improved by placing the components of the photoresist in a deliberately engineered arrangement with respect to one another within individual photoresist units, or pixels. A photoresist formed of pixels, a “pixelated” photoresist, ensures that the components of the photoresist are uniformly distributed throughout the resist. Also, by forming the photoresist of specifically engineered pixels, each of the pixels containing the active components of the photoresist is of controlled size and symmetry. The control of the distribution of the components and the uniformity of the size and symmetry of the pixels may serve to optimize the performance of the photoresist. Furthermore, the components within each of the pixels may be arranged to optimize photospeed and to minimize diffusion of the photoacid once it is activated.
The main components of a photoresist are a photoacid generator (PAG), a photoimageable species (such as a polymer), a solubility switch to change the solubility of the photoimageable species when activated by the photo-generated acid produced by the photoacid generator, and a quencher to control the activity of the photo-generated acid. The deliberately engineered arrangement of the components places the PAG in close proximity to the switches on the photoimageable species and separates the quencher from the PAG by the photoimageable species. This arrangement ensures that the photospeed of the photoresist is maximized by positioning the PAG in close proximity to the switch on the photoimageable species and by ensuring that the quencher cannot come between the PAG and the switch to reduce the activity of the photogenerated acid before it can react with the switch. This arrangement also ensures that the photogenerated acid does not react with switches on photoimageable species that are beyond the region that has been addressed by radiation. This occurs by surrounding the engineered ensemble of the PAG, switch, and photoimageable species by quencher. Once the photogenerated acid reacts with the switch and deprotects the photoimageable species to thereby change the solubility of the photoimageable species, the photogenerated acid may be neutralized by the basic quencher positioned beyond the photoimageable species.
This deliberately engineered placement and size and symmetry constraint (molecular weight distribution) of the PAG, switch, photoimageable species, and quencher forms individual pixels within the photoresist within which a self-contained reaction occurs to pattern the photoresist. These pixels may take on a variety of forms including a polymer chain, a bulky cluster, a micelle, or a micelle formed of several polymer chains. Furthermore, these pixels may be designed to self-assemble onto the substrate on which the photoresist is formed.
In one embodiment, the pixels may be formed by a polymer chain. The polymer chain may be designed to include individual pixels 100 that pre-organize the arrangement of a photoacid generator (PAG), a photoimageable species having a solubility switch, and a quencher with respect to one another. These individual units are arranged so that the irradiated portions of the polymer chain may break away from the unexposed portions of the chain and form distinct irradiated patterns within the photoresist. In an embodiment, the photoimageable species 105 may be the polymer backbone of the polymer chain as illustrated in
In another embodiment, the polymer chain may be designed to fold into bulky clusters that create individual pixels. The polymer chain in this embodiment folds by self-assembly into a bulky cluster. The self-assembly causes the bulky cluster to be uniformly packed so that the molecular weight distribution of the individual pixels as well as the photoresist as a whole are uniform and as well enforces specific geometry upon the bulky cluster.
In another embodiment, the pixels are formed by a micelle. A micelle is a sphere-shaped complex formed of many individual units having a hydrophilic (water-loving) end and a hydrophobic (water-hating) end. The shape of micelles is due to energy-minimization and thus may be any shape that minimizes energy. The individual units may be formed of covalently bound compounds such as the one illustrated in
The micelle 350 just described in the above embodiment is a standard type of micelle having a hydrophobic interior and a hydrophilic exterior. The micelle 350 may alternatively be a reverse micelle having a hydrophilic interior and a hydrophobic exterior. A reverse micelle 350 may be formed of micellar units such as 300 in
Pixelated photoresists may be used to create patterns for the formation of many structures used in integrated circuits. In one embodiment, a chemically amplified pixelated photoresist may be used to form lines for transistor gates. In another embodiment, a chemically amplified pixelated photoresist may be used to form trenches or vias for interconnect lines. In one embodiment the chemically amplified pixelated photoresists may be used to form both vias and trenches by a conventional dual damascene method. Other applications for forming microelectromechanical machines (MEMS), microfluidics structures, or other small structures are also comprehended. For the sake of simplicity a process of forming only vias will be described.
In
In
In
The pixelated photoresist 420 contains pixels as described above that may be in the form of polymer chains, bulky clusters, or micelles. These pixels each contain a PAG, a photoimageable species having a solubility switch, and a quencher. The pixelated photoresist 420 is formed by solvating the pixels or pixel components within a compatible solvent and by optionally adding additives. The ratio of PAG/photoimageable species/quencher may be in the approximate range of 1/10/1 and 1/100/3. The additives in the photoresist 420 may be any one of or a combination of a plasticizer, a surfactant, adhesion promoter, an acid amplifier, a dissolution inhibitor, a dissolution promoter, a photobase, or a photodecomposable base. The pixels and the additives of the photoresist 420 are mixed with a solvent. The solvent may be non-aqueous, for example, polypropylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, cyclopentanone, heptanone, or cyclohexanone. The solvent, in the situation where the pixels of the photoresist 420 are regular micelles having a hydrophilic surface are solvated, may be polar and/or an aqueous solvent. Examples of polar solvents include alcohols such as butanol, ethanol, and isopropanol, acetone, and water. In another example, water may be used as a polar solvent. An aqueous solvent may be valuable in that water is more environmentally safe than most organic solvents. The choice of solvent depends on the polarity and architecture of the components used to form the photoresist. The amount of solvent is also dependent on the thickness of the photoresist and on the size of the wafer. If a thicker pixelated photoresist 420 is desired then less solvent is used, and if a thinner pixelated photoresist 420 is desired more solvent is used. Also, the larger the wafer the more solvent is used. In a particular embodiment, for the pixelated photoresist 420 used for 248 nm, 193 nm, and EUV (in particular 13.5 nm) the amount of solvent used may be in the approximate range of 1% to 5% by weight solid of the pixelated photoresist 420.
As illustrated in
After the pixelated photoresist 420 is developed, vias 440 are etched through dielectric layer 410 down to substrate 400, as illustrated in
A barrier layer 450 is then formed over the vias 440 and the dielectric 410 as illustrated in
Several embodiments of the invention have thus been described. However, those of ordinary skill in the art will recognize that the invention is not limited to the embodiments described, but can be practiced with modification and alteration within the scope and spirit of the appended claims that follow.
Claims
1. A composition, comprising:
- a photoacid generator;
- a photoimageable species having a solubility switch; and
- a quencher, wherein the photo-acid generator, the photoimageable species having the solubility switch, and the quencher are in a deliberately engineered arrangement consisting of a chain with respect to one another to define a unit of the composition.
2. The composition of claim 1, wherein the deliberately engineered arrangement places the photo-acid generator in close proximity to the photoimageable species having the solubility switch and separates the quencher from the photoacid generator by the photoimageable species having the solubility switch.
3. The composition of claim 2, wherein the quencher surrounds a core formed of the photoimageable species surrounding the photoacid generator.
4. The composition of claim 2, wherein the solubility switch points in the direction of the photoacid generator.
5. The composition of claim 1, wherein the photoimageable species is the backbone of the chain.
6. The composition of claim 1, wherein the photoacid generator and the quencher are bound to the photoimageable species.
7. The composition of claim 1, wherein the photoimageable species are linked to one another by a linker containing a switch.
8. A composition, comprising:
- a plurality of pixels of the same size, wherein the pixels each comprise a photo-acid generator, a photoimageable species having a solubility switch, and a quencher in a deliberately engineered arrangement consisting of a chain.
9. The composition of claim 8, further comprising a solvent to solvate the plurality of pixels.
10. The composition of claim 8, further comprising additives to prevent a bulk phase of the plurality of pixels.
11. The composition of claim 8, wherein the composition further comprises a binding group to bind the pixel to a substrate.
12. A photoresist, comprising:
- at least one photoacid generator selected from the group consisting of diaryliodonium, triaryliodonium, an arylsulfonium, a perflate, a nonaflate, or a hydrocarbon sulfonate;
- at least one quencher selected from the group consisting of tetrabutylammonium hydroxide, collidine, analine, or dimethylaminopyridine; and
- a photoimageable species, wherein the photoacid generator, the quencher and the photoimageable species are in a deliberately engineered arrangement with respect to one another to define a unit of the composition and wherein the photoacid generator and the photoimageable species form a micelle such that the micelle is arranged to place one of the photoacid generator and the quencher in a center of the micelle and one of the photoacid generator and the quencher on a periphery of the micelle wherein the photoacid generator is separated from the quencher by the photoimageable species.
13. The photoresist of claim 12, further comprising a solubility switch on the photoimageable species.
14. The photoresist of claim 12, further comprising a solubility switch placed in between the photoacid generator and the photoimageable species.
15. The photoresist of claim 12, wherein the photoacid generator, the photoimageable species, and the quencher are bound by one of ionic forces, covalent bonds, hydrogen bonds, or hydrophobic forces.
16. The photoresist of claim 12, wherein the micelle further comprises a binding group to bind the micelle to a substrate.
17. The photoresist of claim 12, wherein the micelle comprises a hydrophilic exterior and a hydrophobic interior.
18. The photoresist of claim 12, wherein the micelle is a reverse micelle comprising a hydrophobic exterior and a hydrophilic interior.
19. The photoresist of claim 17, wherein the micelle is dispersed within an aqueous solution.
20. A method, comprising:
- combining a plurality of components of a photoresist to self assemble the plurality of components into a plurality of pixels within a pixelated photoresist, wherein the plurality of components comprises a photoacid generator selected from the group consisting of diaryliodonium, triaryliodonium, an arylsulfonium, a perflate, a nonaflate, or a hydrocarbon sulfonate, a photoimageable species having a solubility switch, and a quencher selected from the group consisting of tetrabutylammonium hydroxide, collidine, analine, or dimethylaminopyridine in a deliberately engineered arrangement; and
- applying the pixelated photoresist to a substrate.
21. The method of claim 20, wherein combining the plurality of components of the photoresist forms a plurality of pixels having a micellar structure.
22. The method of claim 20, wherein combining the plurality of components of the photoresist forms a plurality of pixels formed as bulky clusters.
23. The method of claim 20, further comprising self-assembling the plurality of pixels to the surface of the substrate.
24. A method comprising:
- applying a pixelated photoresist to a substrate wherein the pixelated photoresist comprises a plurality of pixels, each pixel comprising a photoacid generator selected from the group consisting of diaryliodonium, triaryliodonium, an arylsulfonium, a perflate, a nonaflate, or a hydrocarbon sulfonate, a photoimageable species having a solubility switch and a quencher selected from the group consisting of tetrabutylammonium hydroxide, collidine, analine, or dimethylaminopyridine in a deliberately engineered arrangement;
- patterning the photoresist by irradiating the photoresist; and
- etching the substrate.
25. The method of claim 24, wherein applying a photoresist to the substrate comprises applying a chemically amplified photoresist to the substrate.
26. The method of claim 24, wherein patterning the photoresist by irradiating the photoresist comprises exposing the photoresist to light having a wavelength of 193 nm.
27. The method of claim 24, wherein patterning the photoresist by irradiating the photoresist comprises exposing the photoresist to light having a wavelength in the extreme ultraviolet region of the spectrum.
28. The method of claim 27, wherein the wavelength in the extreme ultraviolet region of the spectrum is 13.5 nm.
29. The composition of claim 1, wherein (a) the photoimageable species including the solubility switch has at least one first type of side chain and (b) the photoacid generator is associated with the first type of side chain and spatially proximal to the photoimageable species.
30. The composition of claim 29, further comprising at least one second type of side chain on the photoimageable species wherein the quencher is associated with the second type of side chain and spatially distal from the photoimageable species.
31. The composition of claim 29, wherein the photoimageable species further comprises a first polymer and a linker polymer.
32. The composition of claim 31, further comprising a second polymer covalently bonded to the linker and having at least one second type of side chain, wherein the quencher is associated with a second type of side chain and spatially distal from the second polymer.
33. The composition of claim 30, wherein the photoimageable species including the solubility switch, the photoacid generator and the quencher form a unit.
34. The composition of claim 33, wherein the units are identical.
35. The composition of claim 34, wherein the composition has a property such that upon exposure to an imaging source, a chain of units are covalently bonded by linker polymers.
36. The composition of claim 32, wherein the photoimageable species including the solubility switch, the photoacid generator, the quencher and the second polymer form a unit.
37. The composition of claim 36, wherein the units are identical.
38. The composition of claim 37, wherein the composition has a property such that upon exposure to an imaging source, a chain of units are covalently bonded by linker polymers.
39. The composition of claim 1, wherein the photoimageable species comprises a first polymer and a linker polymer, wherein the solubility switch is associated with the linker polymer.
40. The composition of claim 39, wherein the first polymer is selected from the group consisting of a carborane, a steroid, an alicyclic hydrocarbone, polyhedral oligosilsequioxane, colloidal silica, a micelle and a carbon moiety having a diameter less than 2 nm.
41. The composition of claim 40, wherein (a) the photoacid generator is associated with the linker polymer by at least one first type of side chain and spatially proximal to the linker polymer and (b) the quencher is associated with the first polymer by at least one second type of side chain and spatially distal from the first polymer.
42. The composition of claim 41, wherein the photoimageable species, the photoacid generator and the quencher form a unit.
43. The composition of claim 42, wherein the composition has a property such that upon exposure to an imaging source, a multitude of units are covalently linked by the linker polymer.
44. The composition of claim 43, wherein the units are adapted to form a cluster such that each photoacid generator resides in a center of the cluster, each first polymer resides spatially outward from the photoacid generators and each quencher resides spatially outward from each first polymer.
45. The composition of claim 1, wherein the photoimageable species is covalently linked to the solubility switch and the solubility switch is covalently linked to the photoacid generator.
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Type: Grant
Filed: Sep 30, 2004
Date of Patent: Aug 23, 2011
Patent Publication Number: 20060068318
Assignee: Intel Corporation (Santa Clara, CA)
Inventors: Robert P. Meagley (Emeryville, CA), Michael D. Goodner (Hillsboro, OR), Bob E. Leet (Scottsdale, AZ), Michael L. McSwiney (Hillsboro, OR)
Primary Examiner: Amanda C. Walke
Attorney: Blakely, Sokoloff, Taylor & Zafman LLP
Application Number: 10/956,284
International Classification: G03F 7/00 (20060101); G03F 7/004 (20060101); G03F 7/029 (20060101); G03F 7/26 (20060101);